CN116218077B - Halogen-free flame-retardant master batch, halogen-free flame-retardant composite material, and preparation methods and applications thereof - Google Patents
Halogen-free flame-retardant master batch, halogen-free flame-retardant composite material, and preparation methods and applications thereof Download PDFInfo
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- CN116218077B CN116218077B CN202211706419.XA CN202211706419A CN116218077B CN 116218077 B CN116218077 B CN 116218077B CN 202211706419 A CN202211706419 A CN 202211706419A CN 116218077 B CN116218077 B CN 116218077B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 153
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 polypropylene Polymers 0.000 claims abstract description 46
- 239000004743 Polypropylene Substances 0.000 claims abstract description 44
- 229920001155 polypropylene Polymers 0.000 claims abstract description 44
- 239000004611 light stabiliser Substances 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- 239000011574 phosphorus Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 23
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 23
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 238000012360 testing method Methods 0.000 claims abstract description 8
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 10
- 238000005187 foaming Methods 0.000 abstract description 6
- 230000035939 shock Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 239000007921 spray Substances 0.000 description 13
- 239000002352 surface water Substances 0.000 description 13
- 239000003963 antioxidant agent Substances 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 10
- 238000010998 test method Methods 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 2
- 241000192710 Microcystis aeruginosa Species 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920005633 polypropylene homopolymer resin Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a halogen-free flame-retardant master batch, a halogen-free flame-retardant composite material, and a preparation method and application thereof. The halogen-free flame-retardant master batch comprises the following components in parts by weight: 10-15 parts of polypropylene resin, 60-80 parts of metal hydroxide flame retardant, 6-10 parts of phosphorus flame retardant and 0.3-1 part of light stabilizer; the melting point of the phosphorus flame retardant is 40-100 ℃, and the testing method is GB/T19466.3-2004; the metal hydroxide flame retardant is aluminum hydroxide; the light stabilizer is a NOR type hindered amine light stabilizer. The halogen-free flame-retardant composite material prepared by the invention not only can reach the flame retardant property of V-2, but also has better shock resistance on the premise of lower addition amount of the aluminum hydroxide flame retardant, thereby improving the appearance problems of particle foaming and the like of the halogen-free flame-retardant composite material.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a halogen-free flame-retardant master batch, a halogen-free flame-retardant composite material, and a preparation method and application thereof.
Background
The polypropylene has the advantages of low density, good heat insulation performance, good sound insulation performance and the like, has been widely applied to industries such as automobiles, household appliances and the like, and the high polymer polypropylene is burnt vigorously when meeting fire, has an oxygen index of 17-18, greatly limits the application range of the polypropylene, and needs to be modified by adding a flame retardant to improve the flame retardant property. In order to better disperse the flame retardant in the polypropylene system, the flame retardant is typically added to the polypropylene composite in the form of flame retardant masterbatch.
The flame retardants commonly used in the flame retardant master batches are classified into two main types of halogen and halogen-free flame retardant, wherein the halogen flame retardants have great influence on the environment, and part of the flame retardants are classified as forbidden products, so that development of halogen-free flame retardant products is urgently needed. Wherein the metal hydroxide flame retardant belongs to a common halogen-free flame retardant, and the flame retardant mechanism of the metal hydroxide flame retardant is as follows: (1) The polymer material is heated and decomposed at high temperature to release crystal water, and a large amount of heat is absorbed from a combustion zone, so that the temperature rise of the polymer material is restrained, the thermal decomposition of the polymer material is delayed, and the combustion speed is reduced; (2) The water vapor generated by decomposition dilutes the combustible gas and O 2 Is capable of preventing combustion from proceeding; (3) The stable oxide generated by decomposition covers the surface of the combustible material, plays a certain role of heat insulation and can cut off O 2 And the supply of the combustible gas is stopped, thereby playing a role of flame retardance.
The flame retardant property of the polypropylene composite material is enhanced along with the increase of the addition amount of the metal hydroxide flame retardant, and when the addition amount of the metal hydroxide flame retardant is more than 50%, the polypropylene composite material can have a certain flame retardant effect, the flame retardant effect can reach V-2, but the metal hydroxide with high addition amount is easy to decompose and can generate moisture, so that the product particles are foamed, and the surface water bloom is serious; in addition, the high addition amount of the metal hydroxide flame retardant can also lead to the weakening of the impact resistance of the polypropylene composite material, and the quality stability of the product is poor.
Disclosure of Invention
Aiming at the prior art problems, the primary aim of the invention is to provide the halogen-free flame-retardant master batch and the composite material thereof, which not only can achieve the flame retardant performance of V-2, reduce the water spray area, solve the appearance problems of particle foaming and the like, but also have better shock resistance on the premise of low addition of the flame retardant aluminum hydroxide.
The second aim of the invention is to provide a preparation method of the halogen-free flame-retardant master batch.
The third object of the invention is to provide a halogen-free flame-retardant composite material containing the halogen-free flame-retardant master batch.
The fourth object of the invention is to provide an application of the halogen-free flame-retardant master batch or the halogen-free flame-retardant composite material in the field of office supplies.
In order to achieve the above object, the present invention is realized by the following technical scheme:
the halogen-free flame-retardant master batch comprises the following components in parts by weight: 10-15 parts of polypropylene resin, 60-80 parts of metal hydroxide flame retardant, 6-10 parts of phosphorus flame retardant and 0.3-1 part of light stabilizer; the melting point of the phosphorus flame retardant is 40-100 ℃, and the testing method is GB/T19466.3-2004; the metal hydroxide flame retardant is aluminum hydroxide; the light stabilizer is a NOR type hindered amine light stabilizer.
In the process of preparing halogen-free flame retardant master batches or polypropylene composite materials containing metal hydroxide flame retardants, the inventors have found that the metal hydroxide flame retardants cannot effectively reduce the temperature and block the reaction in the initial stage of firing, and the inventors hypothesize that this is probably caused by the higher initial decomposition temperature of the metal hydroxide flame retardants. The inventor finds through research that the decomposition temperature of aluminum hydroxide is similar to the decomposition temperature of the phosphorus flame retardant in the specific melting point range, and in the initial stage of combustion, the aluminum hydroxide can not only absorb hot oxygen faster to decompose and produce water, but also absorb heat further, so that the combustion rate is reduced; and phosphoric acid generated by decomposing the phosphorus flame retardant can also react with aluminum hydroxide to accelerate the generation of water vapor, absorb heat and dilute oxygen. Furthermore, the inventors have found that the triazine ring structure contained in NOR-type hindered amine light stabilizers helps to form a stable state faster than other light stabilizersThe fixed free radical ion can neutralize a small amount of active free radicals generated in the combustion process to terminate the free radical chain reaction. The inventor finds that by selecting phosphorus flame retardant in a specific melting point range to match with aluminum hydroxide and matching with NOR type hindered amine light stabilizer, under the preparation conditions of banburying and single screw extrusion, not only V2 flame retardant grade can be realized, but also impact resistance, flexural modulus of more than 1300MPa and notch impact strength of more than 9KJ/m of polypropylene composite material can be ensured on the premise of low addition (20-35%) of aluminum hydroxide 2 And the surface of the composite material has no particle foaming problem, so that the surface water spray area is greatly improved.
Preferably, the NOR type hindered amine light stabilizer contains a repeating unit represented by formula (i):
5 wherein R is 1 、R 2 Each independently selected from C 1 -C 3 Alkoxy or hydrogen; r is R 3 、R 4 Each independently selected from hydrogen, C 4 -C 8 Alkyl or
Further preferably, the NOR type hindered amine light stabilizer is selected from one of the formula (a) or the formula (B)
Or two, wherein formula (A) has the structural formula:
such compounds are commercially available as Tinuvin NOR 371.
Wherein the structural formula of formula (B) is:
such compounds are commercially available as CHIMASSORB 944FDL.
Preferably, the mass content of the triazine ring in the NOR type hindered amine light stabilizer is 10.5-13%.
Further preferably, the molecular weight of the NOR type hindered amine light stabilizer is 2000 to 4000.
Further, the phosphorus flame retardant is an organic phosphate flame retardant.
Further preferably, the phosphorus-based flame retardant is selected from one or more of resorcinol bis [ di (2, 6-dimethylphenyl) phosphate ], hydroquinone bis (diphenyl phosphate) or triphenyl phosphate.
Preferably, the halogen-free flame retardant master batch also comprises 2-5 parts of water absorbent according to parts by weight.
Further preferably, the water absorbing agent is selected from one or more of anhydrous calcium chloride, calcium oxide or calcium hydroxide.
Preferably, the halogen-free flame retardant master batch further comprises 5-10 parts of low-isotacticity polypropylene resin, wherein the isotacticity of the low-isotacticity polypropylene resin is 30-60%. The polypropylene resin with low isotacticity has lower melting point and higher fluidity, can effectively avoid the problem of local overheating of the polypropylene composite material in the preparation process, can ensure that aluminum hydroxide and other powder are banburying and agglomerated at lower temperature, and is convenient for producing flame-retardant master batches.
Preferably, the halogen-free flame retardant master batch also comprises 0.2 to 0.5 part of high-temperature initiator and/or 0.8 to 1.2 parts of antioxidant according to parts by weight.
Preferably, the high temperature initiator is dicumyl and/or polydicumyl.
Preferably, the antioxidant is a primary antioxidant and/or a secondary antioxidant. Wherein the primary antioxidant may be a hindered phenolic antioxidant, including but not limited to antioxidant 1010; wherein the secondary antioxidant may be a phosphite antioxidant, including but not limited to antioxidant 168.
In addition, the invention also claims a preparation method of the halogen-free flame-retardant master batch, which comprises the steps of mixing polypropylene resin, a metal hydroxide flame retardant, a phosphorus flame retardant and a light stabilizer, heating and banburying, and extruding the banburying mixture through a single screw to obtain the flame-retardant master batch.
As an alternative specific embodiment, the invention also provides a preparation method of the halogen-free flame-retardant master batch, which comprises the steps of mixing polypropylene resin, metal hydroxide flame retardant, phosphorus flame retardant, light stabilizer and low-isotacticity polypropylene resin, heating and banburying, adding water absorbent to continue banburying after the banburying is uniform, and extruding the banburying mixture through a single screw to obtain the halogen-free flame-retardant master batch.
Preferably, the banburying temperature is 130-150 ℃; the temperature of the single screw extrusion is 140-160 ℃. The inventor finds that the internal mixing and single screw extrusion mode is used for preparing the flame-retardant master batch, the internal mixer can realize resin melting at a lower temperature, the shearing stress is lower, and the decomposition of aluminum hydroxide caused by overlarge shearing stress can be avoided.
In addition, the invention also claims a halogen-free flame-retardant composite material, which comprises the halogen-free flame-retardant master batch and thermoplastic resin in parts by weight, wherein the mass ratio of the thermoplastic resin to the flame-retardant master batch is 100-200: 100.
preferably, the thermoplastic resin is a homo-polypropylene resin and/or a co-polypropylene resin.
Further preferably, the polypropylene resin has a melt index of 0.5-60 g/10min at 230 ℃/2.16kg, and the test method is GB/T3682-2000.
Further preferably, the polypropylene resin has a melt index of 10 to 20g/10min at 230 ℃/2.16 kg.
Further, the invention also provides a preparation method of the halogen-free flame-retardant composite material, and the halogen-free flame-retardant master batch is mixed with thermoplastic resin to obtain the halogen-free flame-retardant composite material.
Furthermore, the invention also provides application of the halogen-free flame-retardant master batch or the halogen-free flame-retardant composite material in the field of office supplies. Such as components used in copiers as flame retardant materials.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a halogen-free flame-retardant master batch and a composite material thereof, which are prepared by selecting special materialsThe phosphorus flame retardant in the range of the fixed melting point is matched with aluminum hydroxide and matched with NOR type hindered amine light stabilizer, under the preparation conditions of banburying and single screw extrusion, the V2 flame retardant grade can be realized on the premise of low addition amount (20-35%) of aluminum hydroxide, the flexural modulus of the polypropylene composite material is more than 1300MPa, and the notch impact strength is more than 9KJ/m 2 The impact resistance of the polypropylene composite material is ensured, the surface of the composite material has no particle foaming problem, and the surface water spray area is greatly improved.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Examples and comparative examples raw material description:
polypropylene 1: the isotacticity of the polypropylene is more than 90%, the melt index of the polypropylene under the condition of 230 ℃/2.16kg is 9g/10min, and the test method is GB/T3682-2000; EP300M-Z, zhonghai Shell.
Polypropylene 2: the low isotacticity polypropylene resin has an isotacticity of 35%, a melting temperature of 80 ℃, a melt index of 50g/10min under the condition of 230 ℃/2.16kg, and a test method of GB/T3682-2000, with the brand L-MODU S901, and is prepared in Japan.
Metal hydroxide flame retardant 1: aluminum hydroxide, AH-01DG, super nonmetallic material in Luoyang.
Metal hydroxide flame retardant 2: magnesium hydroxide, aitemag 12FD, jiangsu Ai Teke flame retardant material.
Phosphorus flame retardant 1: resorcinol bis [ di (2, 6-dimethylphenyl) phosphate ], melting point 92 ℃, PX-200, japan eight chemistry.
Phosphorus flame retardant 2: hydroquinone bis (diphenyl phosphate) with a melting point of 90 ℃ and WSFR-PX-220, the science and technology of Zhejiang Ten thousand.
Phosphorus flame retardant 3: triphenyl phosphate, melting point 50 ℃, WSFR-TPP, zhejiang Wansheng technology.
Phosphorus flame retardant 4, melamine polyphosphate, melting point > 325 ℃, BUDIT 3141, bodheim chemistry.
Water absorbing agent: anhydrous calcium chloride, 94% content, shandong sea group.
Light stabilizer 1: NOR type hindered amine light stabilizer, CHIMASSORB 944FDL, triazine ring mass content of 11.2%, molecular weight of 2000-3100, and Basff.
Light stabilizer 2: a non-NOR type hindered amine light stabilizer, light stabilizer-UV-3808 PP5, a threo group.
Light stabilizer 3: benzophenone light stabilizer, UV-531, cyanogen specialty.
Light stabilizer 4: NOR type hindered amine light stabilizer, tinuvin NOR 371, triazine ring mass content of 10.5%, molecular weight of 2800-4000, basf.
An antioxidant: antioxidant 1010, commercially available.
Antioxidant 168, commercially available.
High temperature initiator: 2, 3-dimethyl-2, 3-diphenylbutane, commercially available.
The components (e.g., antioxidants, high temperature initiators) selected for each of the parallel examples and comparative examples are the same commercially available products, unless otherwise specified.
Examples 1 to 11
The parts by weight of the raw materials used in the examples below are shown in Table 1.
The following examples use the same preparation method, and the specific steps include:
(1) Weighing polypropylene resin, low-isotacticity polypropylene resin, metal hydroxide flame retardant, phosphorus flame retardant, light stabilizer, antioxidant and high-temperature initiator according to the parts by weight of table 1, adding into an internal mixer, banburying for 10min at 130-150 ℃, adding water absorbent after uniformly mixing, continuously banburying for 5min, adding into a single screw extruder after uniformly mixing, controlling the extrusion temperature at 140-160 ℃, controlling the rotating speed at 150-300 rpm, controlling the current at 70-80%, and obtaining flame-retardant master batch by means of extrusion and die face hot cutting;
(2) And mixing the flame-retardant master batch with polypropylene resin according to the weight portion ratio of the table 1 to obtain the halogen-free flame-retardant composite material.
Comparative examples 1 to 8
The parts by weight of the raw materials used in each comparative example below are shown in Table 2.
Comparative examples 1 to 3 and comparative examples 5 to 8 were prepared in the same manner as in example 1.
Comparative example 4 differs from example 1 in that: weighing polypropylene resin and gold according to the weight parts of table 1
The flame retardant belongs to hydroxide flame retardant, phosphorus flame retardant, light stabilizer, antioxidant and high temperature initiator, and after being uniformly mixed in a high-speed mixer, the flame retardant is added into a material with an aspect ratio of 40:1, controlling the rotating speed at 200-300 rpm, controlling the temperature at 180-200 ℃, extruding, and obtaining the halogen-free flame-retardant composite material.
Table 1 shows the formulation components of the examples: TABLE 1
Table 2 shows the formulation components of each comparative example:
TABLE 2
The halogen-free flame retardant composite materials prepared by the above examples and comparative examples were tested according to the following test method:
flexural modulus (MPa): the test is carried out by adopting a GB/T9341-2008 test method.
IZOD notched impact Strength (KJ/m) 2 ): the test was performed using the ISO 180-2000 test method.
Flame retardancy (UL-94@1.5mm): the GB/T2408-2008 test method is adopted for testing.
Glow wire ignition temperature (gwit@2mm): the test was performed using the IEC 60695-2-13-2010 test method.
The water spray area ratio: uniformly mixing 1 part of black seeds with 100 parts of finished products, then injection molding the mixture into a square plate, scanning the square plate into a photo, introducing the photo into Image J software, screening white pixel points according to different contrast ratios, and counting the proportion of the number of the white pixel points in all the pixel points to obtain the water spray area proportion.
Particle foaming conditions: the particle shrinkage holes are not more than 1 and are normal, the shrinkage holes are >2, the number of the expanded particles is not less than 1, and the particle expansion in the production process is shown.
The raw material compositions and the prepared flame retardant reinforced polypropylene composite property data of the above examples and comparative examples are shown in the following tables 3 and 4:
TABLE 3 Table 3
TABLE 4 Table 4
As can be seen from the above examples, the halogen-free flame retardant composite material prepared by the method can realize V2 flame retardant grade, the flexural modulus of the polypropylene composite material is more than 1300MPa, and the notch impact strength is more than 9KJ/m on the premise of low addition amount (20-35%) of aluminum hydroxide 2 The impact resistance of the polypropylene composite material is ensured, the composite material has no particle foaming problem, and the surface water bloom problem is greatly improved.
From examples 2 and 3, it is apparent that the mass ratio range of the thermoplastic resin to the flame retardant masterbatch is preferable to significantly reduce the surface water spray area of the halogen-free flame retardant composite material.
From examples 4 and 5, it is understood that the addition of the low isotacticity polypropylene resin and the water absorbing agent alone can effectively reduce the surface water spray area of the halogen-free flame retardant composite material. As can be seen from examples 7 to 10, the low isotacticity polypropylene resin and the water absorbent have a synergistic interaction, and can play a role in further reducing the surface water spray area in the halogen-free flame retardant composite material, and the halogen-free flame retardant composite material in examples 7 to 10 has no surface water spray.
As can be seen from comparative example 1, when the aluminum hydroxide content in the halogen-free flame-retardant composite material is low, the mechanical property of the halogen-free flame-retardant composite material is obviously reduced, and the flame retardant property is also NR only; in addition, the surface water spray area of the composite material is also greatly increased.
As is clear from comparative examples 2 and 5, when the halogen-free flame retardant composite material lacks the phosphorus flame retardant and the NOR type hindered amine light stabilizer, the flame retardant property of the composite material is NR, and the surface water spray area is greatly increased.
As is clear from comparative example 3, the flame retardant performance of the composite material prepared using magnesium hydroxide as the metal hydroxide flame retardant of the halogen-free flame retardant composite material was NR.
As can be seen from comparative example 4, the halogen-free flame retardant master batch prepared by the method can greatly improve the mechanical property of the halogen-free flame retardant composite material, greatly improve the surface water spray problem of the composite material, and can enable the flame retardant property of the composite material to reach V-2.
Comparative example 6 is a comparative example using a phosphorus flame retardant having a melting point of more than 120 ℃, and it is understood from the data that the melting point of the phosphorus flame retardant affects the notched impact strength, the surface water mark area, and the flame retardant property of the composite material.
The data of comparative examples 7 and 8 show that the NOR type hindered amine light stabilizer can reduce the surface water spray area in the composite material and improve the flame retardant property of the composite material.
The foregoing examples are illustrative only and are provided to illustrate some of the features of the methods of the present invention. The claims that follow are intended to claim the broadest possible scope as conceivable and the embodiments presented herein are demonstrated for the applicant's true test results. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.
Claims (8)
1. The halogen-free flame-retardant master batch is characterized by comprising the following components in parts by weight: 10-15 parts of polypropylene resin, 60-80 parts of metal hydroxide flame retardant, 6-10 parts of phosphorus flame retardant and 0.3-1 part of light stabilizer;
the melting point of the phosphorus flame retardant is 40-100 ℃, and the testing method is GB/T19466.3-2004; the phosphorus flame retardant is selected from one or more of resorcinol bis [ di (2, 6-dimethylphenyl) phosphate ], hydroquinone bis (diphenyl phosphate) or triphenyl phosphate;
the metal hydroxide flame retardant is aluminum hydroxide;
the light stabilizer comprises a repeating unit represented by the formula (I):
（Ⅰ）
wherein R is 1 、R 2 Each independently selected from C 1 -C 3 Alkoxy or hydrogen; r is R 3 、R 4 Each independently selected from hydrogen, C 4 -C 8 Alkyl or；
The molecular weight of the light stabilizer is 2000-4000;
the preparation method of the halogen-free flame-retardant master batch comprises the following steps: mixing polypropylene resin, a metal hydroxide flame retardant, a phosphorus flame retardant and a light stabilizer, heating and banburying, and extruding the banburying mixture through a single screw to obtain flame retardant master batches.
2. The halogen-free flame retardant masterbatch of claim 1 wherein the light stabilizer is selected from one or both of formula (a) or formula (B), wherein formula (a) has the structural formula:
（A）
the structural formula of the formula (B) is as follows:
（B）。
3. the halogen-free flame retardant master batch according to claim 1, further comprising 2-5 parts of water absorbent in parts by weight; the water absorbent is selected from one or more of anhydrous calcium chloride, calcium oxide or calcium hydroxide.
4. The halogen-free flame retardant master batch according to claim 3, further comprising 5-10 parts by weight of low isotacticity polypropylene resin, wherein the isotacticity of the low isotacticity polypropylene resin is 30-60%.
5. The method for preparing the halogen-free flame-retardant master batch according to claim 1, wherein the polypropylene resin, the metal hydroxide flame retardant, the phosphorus flame retardant and the light stabilizer are mixed, heated and banburying is carried out, and the banburying mixture is extruded by a single screw to obtain the flame-retardant master batch.
6. The halogen-free flame-retardant composite material is characterized by comprising the halogen-free flame-retardant master batch and thermoplastic resin according to any one of claims 1 to 4 in parts by weight, wherein the mass ratio of the thermoplastic resin to the flame-retardant master batch is 100 to 200:100.
7. the halogen-free flame retardant composite of claim 6, wherein the thermoplastic resin is a polypropylene resin having a melt index of 0.5-60 g/10min at 230 ℃/2.16 kg.
8. Use of the halogen-free flame retardant masterbatch according to any one of claims 1 to 4 or the halogen-free flame retardant composite according to any one of claims 6 to 7 in the field of office supplies.
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